U.S. patent number 4,444,257 [Application Number 06/215,995] was granted by the patent office on 1984-04-24 for method for in situ conversion of hydrocarbonaceous oil.
This patent grant is currently assigned to UOP Inc.. Invention is credited to Laurence O. Stine.
United States Patent |
4,444,257 |
Stine |
April 24, 1984 |
Method for in situ conversion of hydrocarbonaceous oil
Abstract
A process for the in situ conversion of heavy hydrocarbonaceous
crude oil containing indigenous trace metal which comprises heating
said heavy hydrocarbonaceous oil in situ to a hydrocarbon
conversion temperature, contacting the hot hydrocarbonaceous oil
with hydrogen at a pressure from about 200 to about 5000 psig, and
recovering the resulting converted hydrocarbonaceous oil.
Inventors: |
Stine; Laurence O. (Western
Springs, IL) |
Assignee: |
UOP Inc. (Des Plaines,
IL)
|
Family
ID: |
22805232 |
Appl.
No.: |
06/215,995 |
Filed: |
December 12, 1980 |
Current U.S.
Class: |
166/261;
166/302 |
Current CPC
Class: |
E21B
43/243 (20130101) |
Current International
Class: |
E21B
43/16 (20060101); E21B 43/243 (20060101); E21B
043/24 (); E21B 043/243 () |
Field of
Search: |
;166/256,261,272,302,303 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Suchfield; George A.
Attorney, Agent or Firm: Hoatson, Jr.; James R. Cutts, Jr.;
John G. Page, II; William H.
Claims
I claim:
1. A process for the in situ catalytic conversion of a heavy
hydrocarbonaceous crude oil having a gravity of less than about
20.degree. API at 60.degree. F.; a melting point greater than about
100.degree. F. and a trace metal content of from about 5 ppm to
about 50,000 ppm, wherein said trace metals are either vanadium,
nickel, iron or a combination thereof, which process comprises:
(a) injecting ambient air into said crude oil;
(b) igniting said crude oil to consume a portion of tar deposits in
said crude oil to raise the surrounding crude to a temperature in
the range of from about 500.degree. F. to about 1400.degree.
F.;
(c) discontinuing said injection of ambient air;
(d) contacting said hot crude oil in situ with hydrogen at a
pressure of from about 200 to about 5000 psig to catalytically in
situ hydroconvert at least a portion of said crude oil employing as
a catalyst said indigenous vanadium, nickel, iron metals or
combinations thereof in their trace quantities;
and
(c) recovering said hydroconverted crude oil.
2. The process of claim 1 wherein said conversion is performed for
about five minutes to five days.
Description
BACKGROUND OF THE INVENTION
The present invention is directed toward the in situ conversion and
subsequent recovery of heavy hydrocarbonaceous crude oil. Although
conventional crudes may be recovered by pumping and subsequent
enhanced oil recovery procedures, the heavier crude oils which have
been discovered resist the heretofor conventional techniques
utilized for recovery. In any case, the recovery of crude oil is
never complete and the utilization of conventional techniques for
heavy crude recovery is even more bleak. For example, some of the
heaviest crude oil deposits have a conventional recovery rate of
approximately 5 percent. Moreover, such a heavy oil requires
substantial processing in order to yield useful products.
Therefore, in order to recover greater quantities of the heavier
crude oil, I propose to convert these crudes in situ with a
combination of high temperature and high pressure hydrogen and to
recover lighter and therefore more easily recoverable crude oil. In
addition, many of the heavier crudes contain indigenous trace
quantities of metals which may be made to perform a catalytic
function in the conversion of the hydrocarbons to more valuable
products. Such metals include nickel, vanadium, iron, etc. These
metals may occur in a variety of forms. They may exist as metal
oxides or sulfides introduced into the crude oil as metallic scale
or similar particles, or they may exist in the form of
water-soluble salts of such metals. Usually, however, they exist in
the form of stable organometallic compounds, such as metal
porphyrins and the various derivatives thereof.
In addition to organometallic compounds crude oils contain greater
quantities of sulfurous and nitrogenous compounds than are found in
lighter hydrocarbon fractions. For example, a heavy Venezuela crude
also known as Orinoco Tar, having a gravity of 9.9.degree. API at
60.degree. F., contains about 1260 ppm vanadium, 105 ppm nickel, 11
ppm iron, 5.88 weight percent sulfur and about 0.635 weight percent
nitrogen. Reduction in the concentration of the sulfurous and
nitrogenous compounds to the extent that the crude oil is suitable
for further processing is accomplished by conversion to hydrogen
sulfide and ammonia.
BRIEF SUMMARY OF THE INVENTION
The object of the present invention is a process for the in situ
conversion of heavy hydrocarbonaceous crude oil containing
indigenous trace metal which comprises heating said heavy
hydrocarbonaceous oil in situ to a hydrocarbon conversion
temperature, contacting the hot hydrocarbonaceous oil with hydrogen
at a pressure from about 200 to about 5000 psig, and recovering the
resulting converted hydrocarbonaceous oil.
OBJECTS AND EMBODIMENTS OF THE INVENTION
The principal object of the present invention is the enhanced
recovery of heavy hydrocarbonaceous crude oil. Another object of
the invention is to at least partially hydroconvert the heavy crude
oil in situ to aid the recovery thereof. Another object of the
invention is the conversion of organometallic hydrocarbons. Yet
another object is to utilize the indigenous metal compounds as a
catalyst for the in situ hydroconversion of heavy crude oil.
DETAILED DESCRIPTION OF THE INVENTION
As hereinabove stated, the present invention principally involves a
process for the in situ conversion of heavy hydrocarbonaceous crude
oil containing indigenous trace metal which comprises heating said
heavy hydrocarbonaceous oil in situ to a hydrocarbon conversion
temperature, contacting the hot hydrocarbonaceous oil with hydrogen
at a pressure from about 200 to 5000 psig, and recovering the
resulting converted hydrocarbonaceous oil.
Preferred heavy hydrocarbonaceous crude oil for use in the instant
invention are those crudes which do not readily lend themselves to
conventional crude oil recovery; viz., pumping and enhanced oil
recovery techniques. Suitable heavy crudes may have a gravity of
less than about 20.degree. API at 60.degree. F., a melting point
greater than about 100.degree. F., and a trace metal content of
greater than about 5 ppm by weight. Trace metal content of from
about 5 ppm to about 50,000 ppm is suitable for purposes of the
present invention. Suitable sources of heavy crude are found in
such places as the Orinoco Tar Belt deposit in Venezuela, the heavy
crudes of California and the Cold Lake deposits in Canada.
Although the conversion of heavy hydrocarbonaceous crudes is
enhanced by the presence of catalyst, the in situ conversion of a
viscous crude is extremely difficult if not impossible to perform
due to the inability to obtain a homogeneous dispersion of catalyst
throughout the crude oil to be converted. For this reason, the
preferred hydrocarbon crude contains at least trace quantities of
metal which are already in place and act as hydrocarbon conversion
catalyst or catalyst precursors.
The conversion of heavy hydrocarbonaceous crude oil may be
conducted at a temperature from about 400.degree. F. to about
1400.degree. F. and preferably at temperature from about
500.degree. F. to about 900.degree. F. After access to the heavy
crude deposit is made, the crude is heated to reaction or
conversion temperature. Various techniques may be utilized for such
heating such as, for example, contact with super-heated steam, hot
circulating oil, high temperature nitrogen streams, or electrical
heating elements. Another heating technique is to inject air into
the deposit and ignite a portion of the crude to furnish sufficient
heat to increase the temperature of the portion of the crude which
is to undergo hydroconversion.
After the heavy crude oil has been heated to at least about
400.degree. F., elemental hydrogen is introduced to the site of the
heated crude oil and the hydroconversion of the crude is allowed to
proceed. The hydrogen injection stream generally is maintained at a
temperature at least above ambient temperature in order to prevent
or minimize the cooling of the heavy crude deposit below
hydroconversion conditions.
In some cases, it may be advantageous to additionally heat the
heavy crude oil deposit in the presence of hydrogen to ensure the
desired hydroconversion. The process of hydroconversion is
exothermic so that at least a portion of the heat required to
maintain sufficient hydrocarbon conversion conditions is inherently
produced.
In order to accelerate the rate of reaction for the hydroconversion
process and to minimize any coking tendency, the hydroconversion is
conducted at a pressure from about 100 to about 10,000 psig and
preferably at a pressure from about 200 to about 5000 psig.
The amount of time required for the hydroconversion of the heavy
crude oil deposits on the reaction zone temperature, the reaction
zone pressure, the concentration of the indigenous trace metal
which acts as catalyst, specific characteristics of the crude oil
and the degree of conversion desired. Generally, the degree of
conversion is sufficient if the volumetric recovery is
significantly increased but in some cases, more highly refined
crude oil may be desired. In any event, the reaction time in
contact with hydrogen may suitably occur from a few minutes to
several days.
Once the desired crude oil conversion is achieved, the crude is
recovered utilizing conventional techniques known to those skilled
in the art of oil recovery.
The following examples are presented in illustration of a preferred
embodiment of the method of the present invention and are not
intended as an undue limitation on the generally broad scope of the
invention as set out in the appended claims.
EXAMPLE I
Conventional drilling techniques are utilized to gain access to a
deposit of Orinoco Tar having the characteristics presented in
Table I and approximately 5 volume percent of the deposit is
recovered. No further recovery is deemed feasible utilizing
conventional petroleum recovery techniques.
TABLE I ______________________________________ ORINOCO TAR
INSPECTION ______________________________________ Gravity,
.degree.API at 60.degree. F. 9.9 Sulfur, wt. % 5.88 Nitrogen, wt. %
0.635 Heptane Insoluble, wt. % 12.7 Metals, ppm Iron 11 Nickel 105
Vanadium 1260 Distillation IBP, .degree.F. 187 10% 572 30% 840 43%
1000 ______________________________________
EXAMPLE II
The drilling and recovery site of Example I is selected to
demonstrate a preferred embodiment of the present invention. A fire
flood is started in the tar deposit by injecting air and a source
of ignition. A portion of the tar deposit is consumed by fire to
furnish enough heat to raise the surrounding tar to a temperature
of about 850.degree. F. When the desired ambient tar temperature is
reached, in this case 850.degree. F., the air supply is
discontinued in order to extinguish the fire. Then the hot tar
deposit is pressured with hydrogen to approximately 1500 psig and
is permitted to remain at hydroconversion conditions for 48 hours.
During the conversion period, the consumed hydrogen is replenished
to maintain the desired reaction pressure. After the
hydroconversion is performed, an additional 15 volume percent of
the tar deposit is recovered which now has the characteristics
presented in Table II. Additionally for each barrel of tar
produced, about 200 standard cubic feet of light hydrocarbon gases,
including methane, ethane and propane, are recovered.
TABLE II ______________________________________ CONVERTED ORINOCO
TAR INSPECTION ______________________________________ Gravity,
.degree.API at 60.degree. F. 14.0 Sulfur, wt. % 5.0 Nitrogen, wt. %
0.6 Heptane Insoluble, wt. % 11.0 Metals, ppm Iron 10 Nickel 100
Vanadium 1200 Distillation IBP, .degree.F. 170 10% 550 30% 820 50%
1000 ______________________________________
The foregoing specification and examples clearly illustrate the
improvement encompassed by the present invention and the benefits
to be afforded therefrom.
* * * * *